CN1067246A - Novel synthesis process of triethylene diamine - Google Patents
Novel synthesis process of triethylene diamine Download PDFInfo
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- CN1067246A CN1067246A CN 92106206 CN92106206A CN1067246A CN 1067246 A CN1067246 A CN 1067246A CN 92106206 CN92106206 CN 92106206 CN 92106206 A CN92106206 A CN 92106206A CN 1067246 A CN1067246 A CN 1067246A
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- CN
- China
- Prior art keywords
- piperazine
- lewis acid
- compound
- teda
- anhydrous
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002841 Lewis acid Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 16
- PMUNIMVZCACZBB-UHFFFAOYSA-N 2-hydroxyethylazanium;chloride Chemical compound Cl.NCCO PMUNIMVZCACZBB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012442 inert solvent Substances 0.000 claims abstract description 9
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 229940073579 ethanolamine hydrochloride Drugs 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 239000002879 Lewis base Substances 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 5
- 150000007527 lewis bases Chemical class 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- -1 piperazine lewis acid Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract 1
- 150000004885 piperazines Chemical class 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000012188 paraffin wax Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- BNIAKAQSIZOVSN-UHFFFAOYSA-N [Na].CC(O)CO Chemical compound [Na].CC(O)CO BNIAKAQSIZOVSN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- DZNFWGVDYGAMJB-UHFFFAOYSA-K neodymium(3+);phosphate Chemical compound [Nd+3].[O-]P([O-])([O-])=O DZNFWGVDYGAMJB-UHFFFAOYSA-K 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to a new synthesis process of triethylene diamine, which is characterized in that monoethanolamine hydrochloride is used as a starting material, Lewis acid is used as a catalyst, inert solvent or monoethanolamine hydrochloride is used as a solvent, piperazine salt is synthesized at normal pressure by one step, an intermediate is not separated to prepare anhydrous piperazine (PIP), piperazine reacts with ethylene oxide to obtain N-hydroxyethyl piperazine, and the salt reacts at normal pressure in the presence of Lewis acid to obtain triethylene diamine (TEDA). The preparation method is simple, the reaction condition is mild, the catalyst is low in price, the product is single, and the industrial production is facilitated.
Description
The present invention relates to a kind of is raw material by ethanolamine hydrochloride, and piperazine (being called for short PIP) is an important intermediate, the new process of resynthesis triethylenediamine (being called for short TEDA).The chemical name of TEDA is 1,4-diazabicyclo-[2,2,2]-octane (1,4-Diazaicyclo-[2,2,2]-octane be called for short DABCO).
Well-known, Compound P IP and series product thereof are important medicine intermediate, also can be used as the raw material of multiple Chemicals simultaneously; Compound TEDA is the more satisfactory whipping agent of manufacturing urethane foam, and petroleum additive etc.
In view of the importance of this series products, the country of some technology prosperities such as the U.S., Germany, Japan etc. are still very active to the research of its preparation method at present, and operational path is identical substantially, and key is manufacturing and the selection aspect that concentrates on catalyzer.
The present PIP that produces of domestic production factory, all adopting ethanolamine hydrochloride is raw material, ammonium chloride is catalyst, through cyclization, free and make six hydrates of PIP, gets anhydrous PIP through benzene for the method for water again; Because of existing weakness such as technology is loaded down with trivial details, yield is low, environmental pollution is serious, reaction time is long, energy consumption is big, so stop production in succession.Abroad except that Monoethanolamine MEA BASF is raw material, also useful quadrol, diethanolamine, hydroxyethylethylene diamine, diethylenetriamine etc. are carried out the catalysis compressive reaction for raw material, catalyzer is generally rare metal, the reported in literature catalyzer mostly is chromium metal, cobalt, nickel, rhenium etc. in the recent period, and disclosing with nickel or rhenium as U.S. Patent number 4977266 is the method for the synthetic PIP of catalyst.PIP's is synthetic, external most compressive reaction that adopts discloses the method for pressure up to the synthetic PIP of 940 kg/cm as U.S. Patent number 4647701, and the equipment technical qualification require high under this condition of high voltage, investment is big, easily produces explosion hazard and causes hidden danger.Temperature of reaction is generally at 300-450 ℃.Synthetic PIP is as above reacting under the condition, and side reactions such as condensation, cracking, polymerization often take place simultaneously, and when disclosing synthetic PIP as Deutsches Reichs-Patent numbers 3543228, also having nearly, eight kinds of compounds form simultaneously; These by products are very similar to the product physico-chemical property, not only influence yield, also have a strong impact on product separation and treating process, strengthen product cost.
The preparation technology of TEDA since the fifties industrialization, mainly has been to enter just development (seeing " polyurethane industrial " 1991 the 3rd phase 10-12 pages or leaves for details) to some extent of the eighties.The synthetic starting raw material of TEDA mostly is the N-hydroxyethyl piperazine, and other has N, N-dihydroxy ethyl piperazine and N-aminoethyl piperazine etc.Domestic development also has distance because of the selection of processing method and catalyst apart from suitability for industrialized production.The r-Al2O3 of the external up-to-date useful modification of document aspect Preparation of catalysts and selection, acid neodymium phosphate or SrHPO4 and Sr(H2PO4)
2Disclose as U.S. Patent number 4514567, the catalyst cost height that it is selected for use and makes, and need in special tubular reactor to carry out chemical reaction in 320-400 ℃, the lab scale yield can reach more than 80%.Therefore, existing TEDA preparation technology is anxious waits to improve.
The novel process that the purpose of this invention is to provide a kind of synthetic triethylenediamine, its preparation technology is simple, and catalyst is cheap, reaction conditions gentleness under the normal pressure, production cost is low, and the single purity height of product is convenient to suitability for industrialized production.
The object of the present invention is achieved like this: utilize ethanolamine hydrochloride to be starting raw material, at inert solvent or ethanolamine hydrochloride in as solvent, with the Lewis acid is catalyst, under the normal pressure in 250-300 ℃ the reaction synthesizing piperazine lewis acid, intermediate is without separation, in the presence of Lewis base, the treated Piperazine anhydrous that gets, itself and reacting ethylene oxide are formed the N-hydroxyethyl piperazine as intermediate compound, afterwards in inert solvent in the presence of same catalyst, 260-320 ℃ of normal pressure reacts the lewis acid of synthetic triethylenediamine down, again through Louis's alkaline purification, make triethylenediamine at last, raw materials used weight ratio is: ethanolamine hydrochloride: Lewis acid: inert solvent: oxyethane: Lewis base: water: methyl alcohol=1: 0.2-0.4: 1.6-2.2: 0.11-0.13: 0.67-0.73: 0.8-1.0: 0.7-0.8.Louis alkali is OH, RO.The structural formula of Piperazine anhydrous and triethylenediamine is as follows:
Because the present invention is to be starting raw material by ethanolamine hydrochloride, adopt single stage method, Lewis acid with cheapness in inert solvent is a catalyst, carry out chemical reaction under the low condition of normal pressure relative temperature, intermediate makes without separation after the Piperazine anhydrous, with synthetic triethylenediamine under the same catalyst normal pressure, so technology is greatly simplified, the single purity height of product helps suitability for industrialized production.Under normal pressure, react in addition, overcome effectively had under the condition of high voltage of the prior art to the equipment particular requirement and bring the shortcoming of hidden danger, the reaction conditions gentleness, facility investment is few, operational safety.Adopt cheap catalyst, not only raw material sources are easy to get, and have obviously reduced production cost.Therefore, novel process of the present invention is very easily applied.
Chemical equation of the present invention is as follows:
By ethanolamine hydrochloride is starting raw material, is that (Lewis acid is Al to catalyst with the Lewis acid
3+, Mg
2+, Zn
2+, HX etc.), in inert solvents such as a kind of inertia organic heat-carrying agent such as phenyl ether, No. 15 white oils, paraffin or react under the condition of no solvent, temperature remains on 250-300 ℃, finish up to reaction, reactant is dissolved in the suitable quantity of water, leach insolubles and transfer PH5.5-6.5, decompression anhydrate the lewis acid (I) of compound piperazine.The RONa-ROH solution dissolving of (I) and equimolecular quantity refluxes, steam R-OH and steam again in 140-150 ℃, the crystallization of particulate state off-white color, be Compound P IP.Wherein R-is CH3-, C2H5-, HOC3H6-.Again PIP and oxyethane are prepared into compound N-hydroxyethyl piperazine or its lewis acid (II) earlier, (II) is suspended in the inert thermophore, still be that catalyzer reacts under 250-320 ℃ with the Lewis acid, almost quantitative conversion becomes the L salt of compound TEDA, tell thermal barrier, add calculated amount 50% caustic soda, steam the aqueous solution, be controlled at outer the bath at last and steam anhydrous TEDA below 150 ℃.Perhaps tell thermophore adds calculated amount under anhydrous condition RONa-ROH solution, keeping vacuum tightness is that 40mmHg collects distillate, and the R-OH solution that makes compound TEDA uses as whipping agent.
The invention will be further described below in conjunction with embodiment.
Embodiment 1
With Monoethanolamine MEA BASF 61.08 grams (1.00 moles), zinc chloride 1.00 grams, paraffin 120ml adds in the 250ml four-hole bottle, be warming up to more than 200 ℃ under stirring, slowly feed exsiccant HCl gas, generate ethanolamine hydrochloride earlier, continue to feed HCl, 250 ℃ of reaction beginnings heat up, keep 260-280 ℃ of reaction 2 hours, reaction finishes and tells paraffin, adds 50ml water backflow dissolving, the filtering insolubles, filtrate adds 20 and restrains caustic soda dissolving backflow, and decompression is afterwards anhydrated to doing, and gets the crude product of compound (I), the not purified dissolve with methanol solution that can add 27 gram sodium methylates (0.5 mole), reflux, it is clean to steaming to reclaim methyl alcohol, steams white granular crystallization 26.3 grams in 140-150 ℃ again and is anhydrous PIP; Go up to such an extent that PIP adds in the 60ml water with 17.6 gram oxyethane (0.40 mole),, react the fractionation that finishes and dewater to such an extent that 32.6 digest compound (II) in 30-35 ℃ of reaction 2 hours; Add 100ml paraffin afterwards, be warming up to 280-290 ℃, slowly feeding exsiccant HCl gas promptly begins to react, see its reaction end and then tell paraffin, reaction solution adds 50% solution of 10.2 gram caustic soda (0.255 mole), and dissolving refluxes, steam and remove moisture content to doing, under the vacuum tightness of control 30-40mmHg, outer bath temperature distils to such an extent that solid crystal TEDA25.3 restrains 100-150 ℃ of decompression, and total recovery is more than 45%.
Embodiment 2
Monoethanolamine MEA BASF 152.7 grams (2.5 moles), aluminum chloride 2.5 grams are added in the 250ml four-hole bottle, be warming up to more than 200 ℃ under stirring, slowly feed exsiccant HCl gas, generate ethanolamine hydrochloride earlier, be warming up to more than 250 ℃ and continue slowly to feed HCl gas and react approximately and can finish in one hour, add the suitable quantity of water dissolving that refluxes, the filtering insolubles, reduce to filtration drying below 10 ℃ and get PIP dihydrochloride 120 grams, yield is more than 60%.Recycling Mother Solution is applied mechanically.Can make title compound by aforesaid method.
Embodiment 3
Digest compound (II) (0.20 mole) with 26.3 and under agitation be warming up to 280-290 ℃ with 100ml paraffin, slowly feeding exsiccant HCl gas promptly reacts, see its reaction end to after tell paraffin, 50% solution that adds 8.0 gram caustic soda, water purification part is steamed in the dissolving back of refluxing, and reaction product is through gas chromatographic analysis, determine TEDA content, the propylene glycol solution that adds corresponding calculated amount propylene glycol sodium then carries out component distillation, makes the propylene glycol solution of 33%TEDA, yield about 95%.
Embodiment 4
Digest compound (II) with 26.3,1.0 gram zinc chloride and 100ml paraffin under agitation are warming up to 280-290 ℃, slowly feed exsiccant HCl gas and promptly begin reaction, see its reaction end to after tell paraffin, add 50% solution of 16.8 gram caustic soda, stirring makes it abundant neutralization, continues to steam the aqueous solution (containing 2% left and right sides TEDA capable of circulation is raw material), bathing decompression below 150 ℃ then outside distils to such an extent that solid TEDA20.2 restrains yield about 90%.
Claims (6)
1, a kind of process for synthesis of triethylenediamine, it is characterized in that utilizing ethanolamine hydrochloride to be starting raw material, at inert solvent or ethanolamine hydrochloride in as solvent, with the Lewis acid is catalyst, under the normal pressure in 250-300 ℃ the reaction synthesizing piperazine lewis acid, intermediate is without separation, in the presence of Lewis base, the treated Piperazine anhydrous that gets, itself and reacting ethylene oxide are formed the N-hydroxyethyl piperazine as intermediate compound, afterwards in inert solvent in the presence of same catalyst, 260-320 ℃ of normal pressure reacts the lewis acid of synthetic triethylenediamine down, again through Louis's alkaline purification, make triethylenediamine at last, raw materials used weight ratio is: ethanolamine hydrochloride: Lewis acid: inert solvent: oxyethane: Lewis base: water: methyl alcohol=1: 0.2-0.4: 1.6-2.2: 0.11-0.13: 0.67-0.73: 0.8-1.0: 0.7-0.8.
2, technology according to claim 1 is characterized in that Lewis acid is Al
3+, Mg
2+, Zn
2+, HX(represents with L or catalyst L), used Lewis base is OH
-, RO
-
3, technology according to claim 1, it is characterized in that anhydrous PIP is through anhydrous PIP salt, the RONa-ROH solution dissolving backflow with equimolecular quantity steams R-OH, steam anhydrous compound in 140-150 ℃, wherein R-can be CH3-, C2H5-, HOC3H6-.
4, technology according to claim 1 is characterized in that piperazine or its salt and oxyethane are prepared into N-hydroxyethyl piperazine or its lewis acid, and intermediate is prepared compound TEDA without separation.
5, technology according to claim 4 is characterized in that the N-hydroxyethyl piperazine with in the presence of the procatalyst, is prepared into the salt of compound TEDA earlier, under anhydrous condition, adds the RONa-ROH solution dissolving of calculated amount, steam the R-OH solution of compound TEDA.
6, technology according to claim 5 after it is characterized in that making the salt of compound TEDA, is told thermal barrier, 50% soda lye that adds calculated amount, stirring makes it abundant neutralization, continues to steam the aqueous solution, be controlled at then outer bathe decompression below 150 ℃ distil TEDA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106206 CN1067246A (en) | 1992-05-26 | 1992-05-26 | Novel synthesis process of triethylene diamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92106206 CN1067246A (en) | 1992-05-26 | 1992-05-26 | Novel synthesis process of triethylene diamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1067246A true CN1067246A (en) | 1992-12-23 |
Family
ID=4941898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92106206 Pending CN1067246A (en) | 1992-05-26 | 1992-05-26 | Novel synthesis process of triethylene diamine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1067246A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432565A (en) * | 2011-11-10 | 2012-05-02 | 绍兴兴欣化工有限公司 | Preparation method of 2-hydroxyethyl piperazine |
| CN102516094A (en) * | 2011-11-17 | 2012-06-27 | 宁夏东科石化有限公司 | Production method of butyl amide ethenol |
| CN102952024A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethanolamine by using one-step ethylene method |
| JP2014525415A (en) * | 2011-08-26 | 2014-09-29 | ダウ グローバル テクノロジーズ エルエルシー | Improved process for producing alkoxylated piperazine compounds |
-
1992
- 1992-05-26 CN CN 92106206 patent/CN1067246A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102952024A (en) * | 2011-08-24 | 2013-03-06 | 岳阳蓬诚科技发展有限公司 | Method of preparing ethanolamine by using one-step ethylene method |
| JP2014525415A (en) * | 2011-08-26 | 2014-09-29 | ダウ グローバル テクノロジーズ エルエルシー | Improved process for producing alkoxylated piperazine compounds |
| CN102432565A (en) * | 2011-11-10 | 2012-05-02 | 绍兴兴欣化工有限公司 | Preparation method of 2-hydroxyethyl piperazine |
| CN102516094A (en) * | 2011-11-17 | 2012-06-27 | 宁夏东科石化有限公司 | Production method of butyl amide ethenol |
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